Oxidation hair dyes containing 3-aminophenol derivatives, and novel 3-aminophenol derivatives

ABSTRACT

The object of the present patent application are agents for dyeing keratin fibers based on a developer-coupler combination and characterized in that they contain at least one 3-aminophenol derivative of formula (I) or a physiologically compatible, water-soluble salt thereof  
                 
 
     wherein  
     R1 denotes a group of the formula  
                 
 
      or a group of the formula  
                 
 
      as well as novel 3-aminophenol derivatives.

[0001] The present invention relates to agents for oxidative dyeing ofkeratin fibers, particularly human hair, based on a developer/couplercombination containing as the coupler a 3-aminophenol derivativesubstituted in the 6-position, as well as novel 3-aminophenolderivatives substituted in the 6-position.

[0002] Oxidation dyes have attained substantial importance in the fieldof keratin fiber dyeing and particularly hair dyeing. The color isgenerated by reaction of certain developers with certain couplers in thepresence of an appropriate oxidant. The developers used for this purposeare, in particular, 2,5-diaminotoluene, 2,5-diaminophenylethyl alcohol,p-aminophenol, 1,4-diaminobenzene and4,5-diamino-1-(2-hydroxyethyl)pyrazole, whereas suitable couplers are,for example, resorcinol, 2-methylresorcinol, 1-naphthol, 3-aminophenol,m-phenylenediamine, 2-amino-4-(2′-hydroxyethyl)aminoanisole,1,3-diamino-4-(2′-hydroxyethoxy)benzene and 2,4-diamino-5-fluorotoluene.

[0003] In addition to being able to produce colors of the desiredintensity, oxidation dyes used for dyeing human hair must meet numerousadditional requirements. For example, such dyes must be unobjectionablefrom a toxicological and dermatological standpoint, and the haircolorations obtained must be highly resistant to light, permanentwaving, acids and rubbing. In any case, however, in the absence ofexposure to light, rubbing and chemical agents such colorations mustremain stable for a period of at least 4 to 6 weeks. Moreover, it mustbe possible, by a combination of suitable developers and couplers, toproduce a wide range of different color shades.

[0004] Although many couplers are already known, with the currentlyknown colorants it is not possible to meet the requirements placed on acolorant in every respect. Hence, a need continues to exist for novelcouplers that will meet the aforesaid requirements to an especially highdegree.

[0005] We have now found that certain 3-aminophenol derivatives ofgeneral formula (I) meet the requirements placed on couplers to anespecially high degree and with known developers give intense andunusually light-fast and wash-fast color shades.

[0006] Hence, the object of the present invention is an agent for dyeingkeratin fibers, for example wool, furs, feathers or hair, particularlyhuman hair, said agent being based on a developer-coupler combinationand characterized in that it contains at least one 3-aminophenolderivative of formula (I) or a physiologically compatible, water-solublesalt thereof.

[0007] wherein R1 denotes a group of formula (II) or (If)

[0008] wherein R2, R3, R4, R5 and R6 independently of each other denotehydrogen, a halogen atom (F, Cl, Br, I), a cyano group, a hydroxylgroup, a C₁-C₄-alkoxy group, a phenoxy group, a C₁-C₄-hydroxyalkoxygroup, a C₁-C₆-alkyl group, a phenyl group, a C₁-C₄-alkyl thioethergroup, a mercapto group, a nitro group, an amino group, aC₁-C₄-alkylamino group, a hydroxy(C₂-C₄)alkylamino group, adi(C₁-C₄)alkylamino group, a di[hydroxy(C₂-C₄)alkyl]amino group, a[dihydroxy(C₃-C₄)alkyl]amino group, a[hydroxy(C₂-C₄)alkyl]-(C₁-C₄)-alkylamino group, a trifluoromethyl group,a —C(O)H group, a —C(O)CH₃ group, a —C(O)CF₃ group, a —Si(CH₃)₃ group, a(C₁-C₄)-hydroxyalkyl group, a (C₂-C₄)-dihydroxyalkyl group, a(C₁-C₄)-aminoalkyl group or a (C₁-C₄)-cyanoalkyl group, or two adjacentR2 to R6 groups form an —O—CH₂—O— bridge;

[0009] X₁, X₂, X₃, X₄ and X₅ independently of each other denote nitrogenor a C—R7 group, C—R8 group, C—R9 group, C—R10 group or C—R11 group,provided that at least one and at the most three of the X₁ to X₅ groupsdenote nitrogen; and

[0010] R7, R8, R9, R10 and R11 independently of each other denotehydrogen, a halogen atom (F, Cl, Br, I), a cyano group, a (C₁-C₆)-alkylgroup, a (C₁-C₄)-alkyl thioether group, a mercapto group, a nitro group,an amino group. a (C₁-C₄)-alkylamino group, a di(C₁-C₄)alkylamino group,a trifluoromethyl group, a —C(O)H group, a —C(O)CH₃ group, a —C(O)CF₃group, a —Si(CH₃)₃ group, a —C(O)—NH₂ group, a (C₁-C₄)-hydroxyalkylgroup or a (C₂-C₄)-dihydroxyalkyl group.

[0011] Compounds of formula (1) are, for example:

[0012] 4-amino-[1,1′-biphenyl]-2-ol,4-amino-4′-methyl-[1,1′-biphenyl]-2-ol,4-amino-3′-methyl-[1,1′-biphenyl]-2-ol,4-amino-2′-methyl-[1,1′-biphenyl]-2-ol,4-amino-2′,3′-dimethyl-[1,1′-biphenyl]-2-ol,4-amino-2′,4′-dimethyl-[1,1′-biphenyl]-2-ol,4-amino-2′,5′-dimethyl-[1,1′-biphenyl]-2-ol,4-amino-2′,6′-dimethyl-[1,1′-biphenyl]-2-ol,4-amino-3′,4′-dimethyl-[1,1′-biphenyl]-2-ol,4-amino-3′,5′-dimethyl-[1,1′-biphenyl]-2-ol,4-amino-3′,6′-dimethyl-[1,1′-biphenyl]-2-ol,4-amino-2′,4′,5′-trimethyl-[1,1′-biphenyl]-2-ol,4-amino-2′,4′,6′-trimethyl-[1,1′-biphenyl]-2-ol,4-amino-2′,3′,4′-trimethyl-[1,1′-biphenyl]-2-ol,4-amino-2′,3′,5′-trimethyl-[1,1′-biphenyl]-2-ol,4-amino-2′,3′,6′-trimethyl-[1,1′-biphenyl]-2-ol,4-amino-4′-chloro-[1,1′-biphenyl]-2-ol,4-amino-3′-chloro-[1,1′-biphenyl]-2-ol,4-amino-2′-chloro-[1,1′-biphenyl]-2-ol,4-amino-4′-fluoro-[1,1′-biphenyl]-2-ol,4-amino-3′-fluoro-[1,1′-biphenyl]-2-ol,4-amino-2′-fluoro-[1,1′-biphenyl]-2-ol,4-amino-4′-bromo-[1,1′-biphenyl]-2-ol,4-amino-3′-bromo-[1,1′-biphenyl]-2-ol,4-amino-2′-bromo-[1,1′-biphenyl]-2-ol,4-amino-3′,5′-dichloro-[1,1′-biphenyl]-2-ol,4-amino-3′,5′-difluoro-[1,1′-biphenyl]-2-ol,4-amino-3′-bromo-5′-methyl-[1,1′-biphenyl]-2-ol,4-amino-4′-(trifluoromethyl)-[1,1′-biphenyl]-2-ol,4-amino-3′-(trifluoromethyl)-[1,1′-biphenyl]-2-ol,4-amino-2′-(trifluoromethyl)-[1,1′-biphenyl]-2-ol,4-amino-4′-nitro-[1,1′-biphenyl]-2-ol,4-amino-3′-nitro-[1,1′-biphenyl]-2-ol,4-amino-2′-nitro-[1,1′-biphenyl]-2-ol,4-amino-5′-methyl-3′-nitro-[1,1′-biphenyl]-2-ol,4-amino-4′-methyl-3′-nitro-[1,1′-biphenyl]-2-ol,4-amino-2′-methyl-3′-nitro-[1,1′-biphenyl]-2-ol,4-amino-2′-nitro-4′-(trifluoromethyl)[1,1′-biphenyl]-2-ol,4-amino-3′-nitro-5′-(trifluoromethyl)[1,1′-biphenyl]-2-ol,4-amino-3′-nitro-4′-(trifluoromethyl)[1,1′-biphenyl]-2-ol,4-amino-3′-nitro-2′-(trifluoromethyl)[1,1′-biphenyl]-2-ol,4′-amino-2′-hydroxy-[1,1′-biphenyl]4-carbonitrile,4′-amino-2′-hydroxy-[1,1′-biphenyl]-3-carbonitrile,4-amino-4′-methoxy-[1,1′-biphenyl]-2-ol,4-amino-3′-methoxy-[1,1′-biphenyl]-2-ol,4-amino-2′-methoxy-[1,1′-biphenyl]-2-ol,4-amino-4′-ethoxy-[1,1′-biphenyl]-2-ol,4-amino-3′-ethoxy-[1,1′-biphenyl]-2-ol,4-amino-2′-ethoxy-[1,1′-biphenyl]-2-ol,4-amino-3′,4′-dimethoxy-[1,1′-biphenyl]-2-ol,4-amino-3′,5′-dimethoxy-[1,1′-biphenyl]-2-ol,4-amino-2′,3′-dimethoxy-[1,1′-biphenyl]-2-ol,4-amino-2′,4′-dimethoxy-[1,1′-biphenyl]-2-ol,4-amino-2′,5′-dimethoxy-[1,1′-biphenyl]-2-ol,5-amino-2-(1,3-benzodioxol-5-yl)phenol,4-amino-4′-methoxy-3′-methyl-[1,1′-biphenyl]-2-ol,4-amino-4′-methoxy-2′-nitro-[1,1′-biphenyl]-2-ol,4-amino-4′-methoxy-[1,1′-biphenyl]-2-ol,4-amino-4′-phenoxy-[1,1′-biphenyl]-2-ol,4-amino-4′-methylthio-[1,1′-biphenyl]-2-ol,4-amino-3′-methylthio-[1,1′-biphenyl]-2-ol,4-amino-2′-methylthio-[1,1′-biphenyl]-2-ol,4-amino-[1,1′-biphenyl]-2,4′-diol, 4-amino-[1,1′-biphenyl]-2,3′-diol,4-amino-[1,1′-biphenyl]-2,2′-diol,2,2′,3′-trihydroxy-4-amino-[1,1′-biphenyl],2,2′,4′-trihydroxy-4-amino-[1,1′-biphenyl],2,2′,5′-trihydroxy-4-amino-[1,1′-biphenyl],2,2′,6′-trihydroxy-4-amino-[1,1′-biphenyl],2,3′,4′-trihydroxy-4-amino-[1,1′-biphenyl],2,3′,5′-trihydroxy-4-amino-[1,1′-biphenyl],4-amino-2′-methyl-[1,1′-biphenyl]-2,4′-diol,2′,4-diamino-[1,1′-biphenyl]-2-ol, 3′,4-diamino-[1,1′-biphenyl]-2-ol,4,4′-diamino-[1,1′-biphenyl]-2-ol,4′,4-diamino-[1,1′-biphenyl]-2,2′-diol,3′,4-diamino-[1,1′-biphenyl]-2,2′-ol [sic],3′,4-diamino-[1,1′-biphenyl]-2,4′-ol [sic],3′,4-diamino-[1,1′-biphenyl]-2,5′-ol [sic],3′,4-diamino-[1,1′-biphenyl]-2,6′-ol [sic],2′,3′,4-triamino-[1,1′-biphenyl]-2-ol,2′,4,4′-triamino-[1,1′-biphenyl]-2-ol,2′,4,5′-triamino-[1,1′-biphenyl]-2-ol,2′,4,6′-triamino-[1,1′-biphenyl]-2-ol,3′,4,4′-triamino-[1,1′-biphenyl]-2-ol,3′,4,5′-triamino-[1,1′-biphenyl]-2-ol,1-(4′-amino-2′-hydroxy-1,1′-biphenyl-4-yl)ethanone,4-amino-1,1′:3′,1″-terphenyl-2-ol, 4-amino-1,1′:4′,1″-terphenyl-2-ol,4-amino-4′-(aminomethyl)-[1,1′-biphenyl]-2-ol,4-amino-3′-(aminomethyl)-[1,1′-biphenyl]-2-ol,4-amino-2′-(aminomethyl)-[1,1′-biphenyl]-2-ol,(4′-amino-2′-hydroxy-1,1′-biphenyl-4-yl)acetonitrile,(4′-amino-2′-hydroxy-1,1′-biphenyl-3-yl)acetonitrile,(4′2′-hydroxy-1,1′-biphenyl-2-yl)acetonitrile,5-amino-2-(4-pyridinyl)phenol, 5-amino-2-(3-pyridinyl)phenol,5-amino-2-(2-pyridinyl)phenol, 5-amino-2-(3-methyl-2-pyridinyl)phenol,5-amino-2-(4-methyl-2-pyridinyl)phenol,5-amino-2-(5-methyl-2-pyridinyl)phenol,5-amino-2-(6-methyl-2-pyridinyl)phenol,5-amino-2-(3-chloro-2-pyridinyl)phenol,5-amino-2-(4-chloro-2-pyridinyl)phenol,5-amino-2-(5-chloro-2-pyridinyl)phenol,5-amino-2-(6-chloro-2-pyridinyl)phenol,5-amino-2-(3-fluoro-2-pyridinyl)phenol,5-amino-2-(4-fluoro-2-pyridinyl)phenol,5-amino-2-(5-fluoro-2-pyridinyl)phenol,5-amino-2-(6-fluoro-2-pyridinyl)phenol,5-amino-2-(3-trifluoromethyl-2-pyridinyl)phenol,5-amino-2-(4-trifluoromethyl-2-pyridinyl)phenol,5-amino-2-(5-trifluoromethyl-2-pyridinyl)phenol,5-amino-2-(6-trifluoromethyl-2-pyridinyl)phenol,5-amino-2-(3-nitro-2-pyridinyl)phenol,5-amino-2-(4-nitro-2-pyridinyl)phenol,5-amino-2-(5-nitro-2-pyridinyl)phenol,5-amino-2-(6-nitro-2-pyridinyl)phenol,5-amino-2-(2-methyl-3-pyridinyl)phenol,5-amino-2-(4-methyl-3-pyridinyl)phenol,5-amino-2-(5-methyl-3-pyridinyl)-phenol,5-amino-2-(6-methyl-3-pyridinyl)phenol,5-amino-2-(2-chloro-3-pyridinyl)phenol,5-amino-2-(4-chloro-3-pyridinyl)phenol,5-amino-2-(5-chloro-3-pyridinyl)phenol,5-amino-2-(6-chloro-3-pyridinyl)phenol,5-amino-2-(2-bromo-3-pyridinyl)phenol,5-amino-2-(4-bromo-3-pyridinyl)phenol,5-amino-2-(5-bromo-3-pyridinyl)phenol,5-amino-2-(6-bromo-3-pyridinyl)phenol,5-amno-2-(2-nitro-3-pyridinyl)phenol,5-amino-2-(4-nitro-3-pyridinyl)phenol,5-amino-2-(5-nitro-3-pyridinyl)phenol,5-amino-2-(6-nitro-3-pyridinyl)phenol, 5-amino-2-(5-pyrimidinyl)phenoland 5-amino-2-(4-pyrimidinyl)phenol, as well as the physiologicallycompatible, water-soluble salts thereof.

[0013] Preferred compounds of formula (I) are those wherein;

[0014] (i) R1 stands for a group of formula (II) with R2 and R6 denotinghydrogen, or (ii) R1 stands for a group of formula (E) with X₁ and X₅denoting C—R7 and C—R11, with R7 and R11 denoting hydrogen.

[0015] Particularly preferred are the following compounds of formula(1):

[0016] 4-amino-3′-methyl-[1,1′-biphenyl]-2-ol,4-amino-4′-methyl-3′-nitro-[1,1′-biphenyl]-2-ol,4-amino-[1,1′-biphenyl]-2,4′-diol, 5-amino-2-(3-pyridinyl)phenol and5-amino-2-(5-pyrimidinyl)phenol as well as the physiologicallycompatible, water-soluble salts thereof.

[0017] The compounds of formula (I) can be used as the free bases aswell as in the form of their physiologically compatible salts ofinorganic or organic acids, for example hydrochloric acid, sulfuricacid, phosphoric acid, acetic acid, propionic acid, lactic acid orcitric acid.

[0018] The 3-aminophenol derivatives of formula (1) are present in thecolorant of the invention in a total amount from about 0.005 to 20weight percent, an amount from about 0.01 to 5 wt. % and particularlyfrom 0.1 to 2.5 weight percent being preferred.

[0019] Preferred developers are 1,4-diaminobenzene (p-phenylenediamine),1,4-diamino-2-methylbenzene (p-toluylenediamine),1,4-diamino-2,6-dimethylbenzene, 1,4-diamino-3,5-diethylbenzene,1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,3-dimethylbenzene,2-chloro-1,4-diaminobenzene, 1,4-diamino-2-(thiophen-2-yl)benzene,1,4-diamino-2-(thiophen-3-yl)benzene,1,4-diamino-2-(pyridin-3-yl)benzene, 2,5-diaminobiphenyl,1,4-diamino-2-methoxymethylbenzene, 1,4-diamino-2-aminomethylbenzene,1,4-diamino-2-hydroxymethylbenzene,1,4-diamino-2-(2-hydroxyethoxy)benzene,2-[2-(acetylamino)ethoxy]-1,4-diaminobenzene, 4-phenylaminoaniline,4-dimethylaminoaniline, 4-diethylaminoaniline, 4-dipropylaminoaniline,4-[ethyl-(2-hydroxyethyl)amino]aniline,4-[di(2-hydroxyethyl)amino]aniline,4-[di(2-hydroxyethyl)amino]-2-methylaniline,4-[(2-methoxyethyl)amino]aniline, 4-[(3-hydroxypropyl)amino]aniline,4-[(2,3-dihydroxypropyl)amino]aniline,1,4-diamino-2-(1-hydroxyethyl)benzene,1,4-diamino-2-(2-hydroxyethyl)benzene,1,4-diamino-2-(1-methylethyl)benzene,1,3-bis-[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol,1,4-bis-[(4-aminophenyl)amino]butane,1,8-bis-(2,5-diaminophenoxy)-3,6-dioxaoctane, 4-aminophenol,4-amino-3-methylphenol, 4-amino-3-(hydroxymethyl)phenol,4-amino-3-fluorophenol, 4-methylaminophenol,4-amino-2-(aminomethyl)phenol, 4-amino-2-(hydroxymethyl)phenol,4-amino-2-fluorophenol, 4-amino-2-[(2-hydroxyethyl)amino]methylphenol,4-amino-2-methylphenol, 4-amino-2-(methoxymethyl)phenol,4-amino-2-(2-hydroxyethyl)phenol, 5-aminosalicylic acid,2,5-diaminopyridine, 2,4,5,6-tetraminopyrimidine,2,5,6-triamino-4-(1H)-pyrimidone,4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole,4,5-diamino-1-(1-methylethyl)-1H-pyrazole,4,5-diamino-1-[(4-methylphenyl)methyl]-1H-pyrazole,1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazole,4,5-diamino-1-methyl-1H-pyrazole, 2-aminophenol, 2-amino-6-methylphenol,2-amino-5-methylphenol and 1,2,4-trihydroxybenzene.

[0020] Moreover, besides the compounds of formula (I) the colorant ofthe invention can also contain other known couplers, for exampleN-(3-dimethylaminophenyl)urea, 2,6-diaminopyridine,2-amino-4-[(2-hydroxyethyl)amino]anisole,2,4-diamino-1-fluoro-5-methylbenzene,2,4-diamino-1-methoxy-5-methylbenzene,2,4-diamino-1-ethoxy-5-methylbenzene,2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene,2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxybenzene,2,3-diamino-6-methoxypyridine,3-amino-6-methoxy-2-(methylamino)pyridine,2,6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine,1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)benzene,1,3-diamino-4-(2,3-dihydroxypropoxy)benzene,1,3-diamino-4-(3-hydroxypropoxy)benzene,1,3-diamino-4-(2-methoxyethoxy)benzene,2,4-diamino-1,5-di(2-hydroxyethoxy)-benzene,1-(2-aminoethoxy)-2,4-diamino benzene,2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene,2,4-diaminophenoxyacetic acid, 3-[di(2-hydroxyethyl)amino]aniline,4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene,5-methyl-2-(1-methylethyl)phenol, 3-[(2-hydroxyethyl)amino]aniline,3-[(2-aminoethyl)amino]aniline, 1,3-di(2,4-diaminophenoxy)propane,di(2,4-diaminophenoxy)methane, 1,3-diamino-2,4-dimethoxybenzene,2,6-bis-(2-hydroxyethyl)aminotoluene, 4-hydroxyindole,3-dimethylaminophenol, 3-diethylaminophenol, 5-amino-2-methylphenol,5-amino-4-fluoro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol,5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichlorophenol,5-amino-2,4-dichlorophenol, 3-amino-2-methylphenol,3-amino-2-chloro-6-methylphenol, 3-aminophenol,2-[(3-hydroxyphenyl)amino]acetamide,5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol,5-[(2-hydroxyethyl)amino]-2-methylphenol,3-[(2-hydroxyethyl)amino]phenol, 3-[(2-methoxyethyl)amino]phenol,5-amino-2-ethylphenol, 5-amino-2-methoxyphenol,2-(4-amino-2-hydroxyphenoxy)ethanol,5-[(3-hydroxypropyl)amino]-2-methylphenol,3-[(2,3-dihydroxypropyl)amino]-2-methylphenol,3-[(2-hydroxyethyl)amino]-2-methylphenol, 2-amino-3-hydroxypyridine,2,6-dihydroxy-3,4-dimethylpyridine, 5-amino-4-chloro-2-methylphenol,1-naphthol, 2-methyl-1-naphthol, 1,5-dihydroxynaphthalene,1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene,2,7-dihydroxynaphthalene, 2-methyl-1-naphthol acetate,1,3-dihydroxybenzene, 1-chloro-2,4-dihydroxybenzene,2-chloro-1,3-dihydroxybenzene,1,2-dichloro-3,5-dihydroxy-4-methylbenzene,1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline,5-[(2-hydroxyethyl)amino]-1,3-benzodioxole,6-bromo-1-hydroxy-3,4-methylenedioxybenzene, 3,4-diaminobenzoic acid,3,4-dihydro-6-hydroxy-1,4(2H)benzoxazine,6-amino-3,4-dihydro-1,4(2H)benzoxazine, 3-methyl-1-phenyl-5-pyrazolone,5,6-dihydroxyindole, 5,6-dihydroxyindoline, 5-hydroxyindole,6-hydroxyindole, 7-hydroxyindole and 2,3-indolinedione.

[0021] The couplers and developers can be contained in the colorant ofthe invention either individually or in admixture with each other, thetotal amount of couplers and developers in the colorant of the invention(based on the total amount of colorant) being from about 0.005 to 20weight percent, preferably from about 0.01 to 5 weight percent andparticularly from 0.1 to 2.5 weight percent, each.

[0022] The total amount of the developer-coupler combination containedin the colorant described herein is preferably from about 0.01 to 20weight percent, an amount from about 0.02 to 10 weight percent andparticularly from 0.2 to 6 weight percent being especially preferred. Ingeneral, the developers and couplers are used in equimolar amounts.However, it is not disadvantageous if the developers are present in acertain excess or deficiency with respect to such an amount.

[0023] Moreover, the colorant of the invention can also containadditional dye components, for example 6-amino-2-methylphenol and2-amino-5-methylphenol as well as common synthetic or natural directdyes, for example vegetable dyes or synthetic direct dyes from the groupof acid or basic dyes, triphenylmethane dyes, aromatic nitro dyes, azodyes and disperse dyes. The colorants of the invention can contain thesedye components in an amount from about 0.1 to 4 weight percent.

[0024] Naturally, the additional couplers and the developers and otherdye components, provided they are bases, can also be used in the form oftheir physiologically compatible salts of organic or inorganic acids,for example hydrochloric acid or sulfuric acid, or—if they containaromatic OH— groups—in the form of salts of bases, for example as alkaliphenoxides.

[0025] Moreover, if the colorants are used for dyeing hair, they canalso contain common cosmetic additives, for example antioxidants such asascorbic acid, thioglycolic acid or sodium sulfite, as well as perfumeoils, complexing agents, wetting agents, emulsifiers, thickeners andhair-care agents.

[0026] The colorant of the invention can be formulated, for example, asa solution, particularly an aqueous or aqueous-alcoholic solution. Aparticularly preferred formulation, however, is a cream, gel oremulsion. Such a preparation consists of a mixture of dye components andadditives commonly used for such preparations.

[0027] Common additives to solutions, creams, emulsions or gels are, forexample, solvents such as water, lower aliphatic alcohols, for exampleethanol, propanol or isopropanol, glycerol or glycols such as1,2-propylene glycol; moreover wetting agents or emulsifiers from theclasses of anionic, cationic, amphoteric or nonionic surface-activesubstances such as, for example, the fatty alcohol sulfates, ethoxylatedfatty alcohol sulfates, alkylsulfonates, alkylbenzenesulfonates,alkyltrimethylammonium salts, alkylbetaines, ethoxylated fatty alcohols,ethoxylated nonylphenols, fatty alkanolamides and ethoxylated fattyesters; furthermore thickeners such as the higher fatty alcohols,starch, cellulose derivatives, petrolatum, paraffin oil and fatty acids;moreover hair-care agents such as cationic resins, lanolin derivatives,cholesterol, pantothenic acid and betaine. The said constituents areused in amounts commonly employed for such purposes, for example thewetting agents and emulsifiers at a concentration from about 0.5 to 30weight percent, the thickeners in an amount from about 0.1 to 30 weightpercent and the hair-care agents at a concentration from about 0.1 to 5weight percent.

[0028] Depending on the composition, the colorant of the invention canbe weakly acidic, neutral or alkaline. In particular, it has a pH from6.5 to 11.5, the adjustment to a basic value preferably being achievedwith ammonia. However, amino acids and/or organic amines, for examplemonoethanolamine or triethanolamine, or inorganic bases, for examplesodium hydroxide or potassium hydroxide can also be used. For pHadjustment in the acidic range, an inorganic or organic acid, forexample phosphoric acid, acetic acid, citric acid or tartaric acid, canbe used.

[0029] For use in oxidative dyeing of hair, the afore-described colorantis mixed with an oxidant just before use and the resulting mixture isapplied to the hair in an amount sufficient for the hair treatment, ingeneral in an amount from about 60 to 200 grams, depending on thefullness of the hair.

[0030] Suitable oxidants for developing the hair coloration are mainlyhydrogen peroxide or the compounds of addition thereof to urea,melamine, sodium borate or sodium carbonate in the form of a 3 to 12%,preferably 6% aqueous solution. Atmospheric oxygen can also be used. Ifa 6% hydrogen peroxide solution is used as oxidant, the weight ratio ofhair colorant to oxidant is from 5:1 to 1:2 and preferably 1:1. Largeramounts of oxidant are used primarily at higher dye concentrations inthe hair colorant or when more pronounced hair bleaching is wanted atthe same time. The mixture is allowed to act on the hair at 15 to 50° C.for about 10 to 45 minutes, preferably for 30 minutes, after which thehair is rinsed with water and dried. Optionally, following this rinsingthe hair is washed with a shampoo and optionally post-rinsed with a weakorganic acid, for example citric acid or tartaric acid. The hair is thendried.

[0031] The colorant of the invention containing a 3-aminophenolderivative of formula (I) as coupler gives colorations of excellentcolor stability, particularly in terms of light fastness, wash fastnessand rubbing fastness. As far as the coloring properties are concerned,depending on the kind and composition of the dye components, thecolorant of the invention provides a wide range of different colorshades ranging from blond to brown, purple, violet, blue and black. Saidshades are characterized by high color intensity. Furthermore, the verygood coloring properties of the colorant of the present patentapplication are, in particular, characterized by the fact that thiscolorant also makes it possible to dye gray, chemically not previouslydamaged hair with good covering power and without any problems.

[0032] The aminophenol derivatives of formula (I) of the invention canbe prepared by methods of synthesis known from the literature, forexample:

[0033] a) by tetrakis(triphenylphosphine)palladium(0)-catalyzed couplingof a suitably substituted 3-aminophenolboric acid derivative of formula(IV)

[0034]  with a halogen-substituted compound of formula (IIa) or (IIIa)

[0035]  followed by the removal of the protective group needed for thecoupling reaction, or

[0036] b) by tetrakis(triphenylphosphine)palladium(0)-catalyzed couplingof a halogen-substituted 3-aminophenol derivative of formula (V)

[0037]  with a boric acid derivative of formula (IIb) or (IIIb)

[0038]  followed by the removal of the protective group needed for thecoupling reaction, the groups in formulas (IIa), (IIb), (IIIa), (IIIb),(IV) and (V) having the following meaning:

[0039] Ra denotes a protective group as described, for example, in thechapter on “Protective Groups” in Organic Synthesis, chapter 3, WileyInterscience, 1991;

[0040] Rb and Rc independently of each other denote hydrogen or aprotective group as described, for example, in the chapter on“Protective Groups” in Organic Synthesis, chapter 7, Wiley Interscience,1991;

[0041] Rd denotes hydrogen or the two Rd groups together with the—O—B—O— group form an unsubstituted or substituted five-membered orsix-membered cycloaliphatic ring;

[0042] Hal denotes F, Cl, Br or I; and

[0043] R2, R3, R4, R5 and R6 and X₁, X₂, X₃, X₄ and X₅ have the samemeaning as in formulas (II) or (III).

[0044] The 3-aminophenol derivatives of formula (I) are readilywater-soluble and give colorations of excellent color intensity andcolor stability, particularly in terms of light fastness, wash fastnessand rubbing fastness. Moreover, they have excellent storage stabilityparticularly as constituents of the afore-described oxidative colorants.

[0045] Another object of the present invention are novel 3-aminophenolderivatives of the afore-indicated formula (I) or the physiologicallycompatible, water-soluble salts thereof, provided that (i) R1 is not a2-pyridyl group and (ii) R1 is not a 2-hydroxy-4-aminophenyl group.

[0046] The following examples are intended to illustrate the subjectmatter of the invention in greater detail without limiting its scope.

EXAMPLES Examples 1 to 45 Synthesis of 3-aminophenol Derivatives ofGeneral Formula (I)

[0047] A. Synthesis of 3-ethoxymethoxyphenylamine

[0048] A dispersion of 12 g (274.9 mmol) of sodium hydride (55% in oil)was added portionwise at 0° C. to a solution of 20.0 g (183.3 mmol) of3-aminophenol in 450 mL of dried acetonitrile. The mixture was thenallowed to agitate at 0° C. for 3 hours. A solution of 25 g (210.8 mmol)of chloromethyl ethyl ether in 30 mL of acetonitrile was added dropwise,and the mixture was allowed to agitate overnight at room temperature.The reaction mixture was then filtered and the filter cake was washedwith a small amount of acetone. The combined filtrates were evaporated.This gave 32.3 g of 3-ethoxymethoxyphenylamine. The resulting crudeproduct was used in the next step without further purification.

[0049]¹H-NMR (300 MHz, DMSO): δ=6.89 (t, 1H, H5); 6.24 (s, 1H, H2); 6.22(d, 1H); 6.16 (d, 1H); 5.14 (s, 2H, NH₂); 5.11 (s, 2H, OCH₂); 3.75 (q,2H, CH₂); 1.13 (t, 3H, CH₃).

[0050] B. Synthesis of tert butyl N-(3-ethoxymethoxyphenyl)carbamate

[0051] 30 g (180 mmol) of 3-ethoxymethoxyphenylamine from step A and44.4 g (203 mmol) of ditert.butyl dicarbonate were dissolved in amixture of 140 mL of 2N sodium hydroxide and 200 mL of dichloromethane,and the mixture was allowed to agitate for 24 hours at room temperature.The organic phase was then separated, washed to a neutral pH withsaturated aqueous sodium chloride solution, dried over MgSO₄, filteredand evaporated. The resulting crude product was purified on silica gelusing hexane/ethyl acetate (8:1).

[0052] This gave 18 g (42% of the theoretical based on the amount of3-aminophenol used) of tert.butyl N-(3-ethoxymethoxyphenyl)carbamate asa yellow oil.

[0053]¹H-NMR ('300 MHz, DMSO): δ=9.33 (s, 1H, NH); 7.20 (s, 1H, H2);7.14 (t, J=8.0, 1H, H5); 7.05 (d, J=8.0, 1H, H3); 6.63 (d, J=8.0, 1H,H6); 5.17 (s, 2H, OCH₂); 3.64 (q, J=7.1, 2 CH₂); 1.49 (s, 9H,tert.butyl); 1.13 (t, J=7.1, 3H, CH₃), CHN Analysis (C₁₄H₂₁NO₄) % C % H% N Calculated 62.90 7.92 5.24 Found 62.60 8.04 4.97

[0054] C. Synthesis of tert.butylN-(4-bromo-3-ethoxymethoxyphenyl)carbamate

[0055] 13.9 g (52 mmol) of tert.butyl N-(3-ethoxymethoxyphenyl)carbamatefrom step B and 10.2 g (57.2 mmol) of N-bromosuccinimide were dissolvedunder nitrogen in 400 ml, of 1,2-dimethoxyethane, and the solution wasallowed to agitate for 3 hours at room temperature. The reaction mixturewas then poured onto 1000 mL of ice/water and extracted with ethylacetate. The organic phase was washed with a saturated solution ofsodium chloride, dried over magnesium sulfate and filtered and thefiltrate was evaporated. The resulting crude product was purified onsilica gel using hexane/ethyl acetate (4:1).

[0056] This gave 14.4 g (76% of the theoretical) of tert.butylN-(4-bromo-3-ethoxymethoxyphenyl)carbamate as an oil.

[0057]¹H-NMR (300 MHz, DMSO): δ=9.50 (s, 1H, NH); 7.45 (d, J=2.0, 1H,H2); 7.43 (d, J=8.6, 1H, H5); 7.04 (dd, J=2.0, J=8.6, 1H, H6); 5.24 (s,2H, OCH₂); 3.70 (q, J=7.1, 2H, CH₂); 1.48 (s, 9H, tert.butyl); 1.16 (t,J=7.1, 314, CH₃); CHN Analysis (C₁₄H₂₀BrNO₄) % C % H % N Calculated48.57 5.82 4.05 Found 47.82 5.87 3.77

[0058] D. Synthesis of tert.butyl[4-(5,5-dimethyl-[1,3,2]dioxaborinan-2-yl)-3-ethoxymethoxyphenyl]carbamate

[0059] 10 g (28.8 mmol) of tert.butylN-(4-bromo-3-ethoxymethoxyphenyl)carbamate from step C and 13 g (57.6mmol) of 5,5,5′,5′-tetramethyl-2,2′-bi-[1,3,2-dioxaborinane] weredissolved under argon in 260 mL of dioxane. Then, 2.11 g (2.88 mmol) of[1,1′-bis(diphenylphosphino)ferrocene]-dichloropalladium(II) and 8.48 g(86.4 mmol) of potassium acetate were added, and the reaction mixturewas heated at 80° C. for 7 hours. The reaction mixture was then pouredonto 1.6 L of ice/water and extracted with ethyl acetate. The organicphase was washed with saturated aqueous sodium chloride solution, driedover magnesium sulfate and filtered and the filtrate was evaporated. Theresulting crude product was purified on silica gel using hexane/ethylacetate (2:1).

[0060] This gave 5.84 g (54% of the theoretical) of tert.butyl[4-(5,5-dimethyl-[1,3,2]dioxaborinan-2-yl)-3-ethoxymethoxyphenyl]carbamate.

[0061] 1H-NMR (300 MHz, DMSO): δ=9.40 (s, 1H, NH); 7.41 (d, J=8.1, 1H,H5); 7.21 (s, 1H, H2); 7.07 (d, J=8.1, 1H, H6); 5.09 (s, 2H, OCH₂); 3.69(s, 4H, BOCH₂); 3.66 (q, J=7.1, 2H, CH₂); 1.48 (s, 9H, tert.butyl); 1.18(t, 3H, CH₃); 0.95 (s, 6H, CH₃).

[0062] E. Synthesis of the 3-aminophenols of Formula (1)

[0063] 0.23 g (0.6 mmol) of tert.butyl[4-(5,5-dimethyl-[1,3,2]dioxaborinan-2-yl)-3-ethoxymethoxyphenyl]carbamatefrom step D and 0.78 mmol of the appropriate bromo derivative weredissolved under argon in 4 mL of 1,2-dimethoxyethane. Then, 0.07 g (0.06mmol) of tetrakis(triphenylphosphine)palladium and 0.8 mL of 2Npotassium carbonate solution were added, and the reaction mixture washeated at 80° C. At the end of the reaction, the reaction mixture waspoured into 15 mL of ethyl acetate, and the organic phase was extractedwith 1N sodium hydroxide solution and then dried with magnesium sulfate.The solvent was distilled off in a rotary evaporator, and the residuewas purified on silica gel using hexane/ethyl acetate.

[0064] The product thus obtained was dissolved in 2 mL of ethanol and toit was added 1 mL of a 2.9 molar solution of ethanolic hydrochloric acidor of 4-molar hydrochloric acid in dioxane. The reaction mixture wasthen heated at 55° C. At the end of the reaction, the precipitate wasfiltered off, washed with ethanol (or dioxane) and then dried.

[0065] 1. 4-Amino-[1,1′-biphenyl]-2-ol hydrochloride

[0066] Bromo derivative used: bromobenzene

[0067] Yield: 0.041 g (31% of the theoretical)

[0068] ESI-MS: 186 [M+H]⁺ (100)

[0069] 2. 4-Amino-4′-methyl-[1′-biphenyl]-?-ol hydrochloride

[0070] Bromo derivative used: 4-bromotoluene

[0071] Yield: 0.026 g (18% of the theoretical)

[0072] ESI-MS: 200 [M+H]⁺ (100)

[0073] 3. 4-Amino-3′-methyl-[1,1′-biphenyl]-2-ol hydrochloride

[0074] Bromo derivative used: 3-bromotoluene

[0075] Yield: 0.048 g (28% of the theoretical)

[0076] ESI-MS: 200 [M+H]⁺ (100)

[0077]¹-NMR (300 MHz, DMSO): δ=10.15 (s, 1H, OH); 7.31 (s, 1H, H2′);7.29 (m, 3H); 7.13 (d, J=8.1, 1H, H6′); 7.00 (d, J=1.7, 1H, H3); 6.83(dd, J=1.7, J=8.1, 1H, H5); 3.60 (s, br, 3H, NH₃ ⁺); 2.35 (s, 3H, CH₃).

[0078] 4. 4-Amino-2′,3′-dimethyl-[1,1′-biphenyl]-2-ol hydrochloride

[0079] Bromo derivative used: 3-bromo-o-xylene

[0080] Yield: 0.046 g (32% of the theoretical)

[0081] ESI-MS: 214 [M+H]⁺ (100)

[0082] 5. 4-Amino-2′,5′-dimethyl-[1,1′-biphenyl]-2-ol hydrochloride

[0083] Bromo derivative used: 2-bromo-p-xylene

[0084] Yield: 0.046 g (32% of the theoretical)

[0085] ESI-MS: 214 [M+H]⁺ (100)

[0086] 6. 4-Amino-2′,4′-dimethyl-[1-1 biphenyl]—ol hydrochloride

[0087] Bromo derivative used: 6-bromo-m-xylene

[0088] Yield: 0.033 g (17% of the theoretical)

[0089] ESI-MS: 214 [M+H]⁺ (100)

[0090] 7. 4-Amino-3′,4′-dimethyl-[1,1′-biphenyl]-2-ol hydrochloride

[0091] Bromo derivative used: 4-bromo-o-xylene

[0092] Yield: 0.048 g (32% of the theoretical)

[0093] ESI-MS: 214 [M+H]⁺ (100)

[0094] 8. 4-Amino-3′,5′-dimethyl-[1,1′-biphenyl]-2-ol hydrochloride

[0095] Bromo derivative used: 5-bromo-m-xylene

[0096] Yield: 0.021 g (13% of the theoretical)

[0097] ESI-MS: 214 [M+H]⁺ (100)

[0098] 9. 4-Amino-2′,4′,5′-trimethyl-[1,1′-biphenyl]-2-ol hydrochloride

[0099] Bromo derivative used: 5-bromo-1,2,4-trimethylbenzene

[0100] Yield: 0.023 g (14% of the theoretical)

[0101] ESI-MS: 228 [M+H]⁺ (100)

[0102] 10. 4-Amino-4′-chloro-[1,1′-biphenyl]-2-ol hydrochloride,

[0103] Bromo derivative used: 1-bromo-4-chlorobenzene

[0104] Yield: 0.016 g (10% of the theoretical)

[0105] ESI-MS: 220 [M+H]⁺ (100)

[0106] 11. 4-Amino-4′-chloro-[1′-biphenyl]-2-ol hydrochloride

[0107] Bromo derivative used: 1-bromo-3-chlorobenzene

[0108] Yield: 0.036 g (23% of the theoretical)

[0109] ESI-MS: 220 [M+H]⁺ (100)

[0110] 12. 4-Amino-2′-chloro-[1,1′-biphenyl]-2-ol hydrochloride

[0111] Bromo derivative used: 1-bromo-2-chlorobenzene

[0112] Yield: 0.018 g (12% of the theoretical)

[0113] ESI-MS: 220 [M+H]⁺ (100)

[0114] 13. 4-Amino-3′,5′-dichloro-[1,1′-biphenyl]-2-ol hydrochloride

[0115] Bromo derivative used: 1-bromo-3,5-dichlorobenzene

[0116] Yield: 0.074 g (40% of the theoretical)

[0117] ESI-MS: 254 [M+H]⁺ (100)

[0118] 14. 4-Amino-4′-fluoro-[1,1′-biphenyl]-2-ol hydrochloride

[0119] Bromo derivative used: 1-bromo-4-fluorobenzene

[0120] Yield: 0.047 g (33% of the theoretical)

[0121] ESI-MS: 204 [M+H]⁺ (100)

[0122] 15. 4-Amino-3′,5′-difluoro-[1,1′-biphenyl]-2-ol hydrochloride

[0123] Bromo derivative used: 1-bromo-4-fluorobenzene

[0124] Yield: 0.024 g (16% of the theoretical)

[0125] ESI-MS: 220 [M−H]⁺ (100)

[0126] 16. 4-Amino-3′-bromo-5′-methyl-[1,1′-biphenyl]-2-ol hydrochloride

[0127] Bromo derivative used: 3,5-dibromotoluene

[0128] Yield: 0.022 g (12% of the theoretical)

[0129] ESI-MS: 278 [M]⁺ (100)

[0130] 17. 4-Amino-4′-(trifluoromethyl)-[1,1′-biphenyl]2-olhydrochloride

[0131] Bromo derivative used: 1-bromo-4-(trifluoromethyl)benzene

[0132] Yield: 0.017 g (10% of the theoretical)

[0133] ESI-MS: 254 [M+H]⁺ (100)

[0134] 18. 4-Amino-3′-(trifluoromethyl)-[1,1′-biphenyl]-2-olhydrochloride

[0135] Bromo derivative used: 1-bromo-4-(trifluoromethyl)benzene

[0136] Yield: 0.017 g (10% of the theoretical)

[0137] ESI-MS: 254 [M+H]⁺ (100)

[0138] 19. 4-Amino-1′-nitro-[1,1′-biphenyl]-2-ol hydrochloride

[0139] Bromo derivative used: 1-bromo-3-nitrobenzene

[0140] Yield: 0.029 g (18% of the theoretical)

[0141] ESI-MS: 253 [M+Na]⁺ (100)

[0142]¹H-NMR (300 MHz, DMSO): δ=10.40 (s, br, 1H, OH); 8.16 (d, J=8.0,1H, H4′); 8.00 (d, J=8.0, 1H, H6′); 7.72 (dd, J=8.0, J=8.0, 1H, H5′);7.43 (d, J=8.2, 1H, H6); 6.92 (s, 1H, H3); 6.78 (d, J=8.2, 1H, H5); 3.46(s, br, 3H, NH₃ ⁺).

[0143] 20. 4-Amino-4′-methyl-3′-nitro-[1,1′-biphenyl]-2-ol hydrochloride

[0144] Bromo derivative used: 1-bromo-2-nitrotoluene

[0145] Yield: 0.082 g (49% of the theoretical)

[0146] ESI-MS: 267 [M+Na]⁺ (100)

[0147]¹H-NM (300 MHz, DMSO): δ=10.39 (s, br, 1H, OH); 8.16 (d, J=1.7,1H, H2′); 7.81 (dd, J=1.7, J=8.0, 1H, H6′); 7.54, (d, J=8.0, 1H, H5′);7.41 (d, J=8.2, 1H, H6); 6.98 (d, J=1.8, 1H, H3); 6.82 (dd, J=1.8,J=8.1, 11H, H5); 3.46 (s, br, 3H, NH3+); 2.54 (s, 3H, CH₃). CHNAnalysis: (C₁₃H₁₃N₂O₃HCl) % C % H % N % Cl Calculated 55.62 4.67 9.9812.63 Found: 55.10 4.60 9.50 12.20

[0148] 21. 4-Amino-2′-nitro-4′-(trifluoromethyl)[1,1′-biphenyl-2-olhydrochloride

[0149] Bromo derivative used: 1-bromo-2-nitro-4-(trifluoromethyl)benzene

[0150] Yield: 0.057 g (28% of the theoretical)

[0151] ESI-MS: 297 [M−H]⁺ (100)

[0152] 22. 4′-Amino-2′-hydroxy-[1,1′-biphenyl]-1-carbonitrilehydrochloride

[0153] Bromo derivative used: 3-bromobenzonitrile

[0154] Yield: 0.036 g (24% of the theoretical)

[0155] ESI-MS: 233 [M+Na]⁺ (100)

[0156] 23. 4-Amino-4′-methoxy-[1,1′-biphenyl]-2-ol hydrochloride

[0157] Bromo derivative used: 1-bromo-4-methoxybenzene

[0158] Yield: 0.021 g (14% of the theoretical)

[0159] ESI-MS: 216 [M+H]⁺ (100)

[0160] 24. 4-Amino-3′-methoxy-[1,1′-biphenyl]-2-ol hydrochloride

[0161] Bromo derivative used: l-bromo-3-methoxybenzene

[0162] Yield: 0.01 g (7% of the theoretical)

[0163] ESI-MS: 216 [M+H]⁺ (100)

[0164] 25. 4-Amino-2′-methoxy-[1,1′-biphenyl]-2-ol hydrochloride

[0165] Bromo derivative used: 1-bromo-2-methoxybenzene

[0166] Yield: 0.058 g (36% of the theoretical)

[0167] ESI-MS: 214 [M−H]⁺ (100)

[0168] 26. 4-Amino-4′-ethoxy-[1,1′-biphenyl]-2-ol hydrochloride

[0169] Bromo derivative used: 1-bromo-4-ethoxybenzene

[0170] Yield: 0.020 g (13% of the theoretical)

[0171] ESI-MS: 230 [M+H]⁺ (100)

[0172] 27. 4-Amino-2′,4′-dimethoxy-[1,1′-biphenyl]-2-ol hydrochloride

[0173] Bromo derivative used: 1-bromo-2,4-dimethoxybenzene

[0174] Yield: 0.050 g (30% of the theoretical)

[0175] ESI-MS: 268 [M+Na]⁺ (100)

[0176] 28. 4-Amino-2′,5′-dimethoxy-[1,1′]-2-biphenyl]-2-ol hydrochloride

[0177] Bromo derivative used: 2-bromo-1,4-dimethoxybenzene

[0178] Yield: 0.061 g (36% of the theoretical)

[0179] ESI-MS: 268 [M+Na]⁺ (100)

[0180] 29. 5-Amino-2-(1,3-1-benzodioxo-5-yl)phenol hydrochloride

[0181] Bromo derivative used: 5-bromo-1,3-benzodioxol

[0182] Yield: 0.030 g (19% of the theoretical)

[0183] ESI-MS: 230 [M+H]⁺ (100)

[0184]¹H-NMR (300 MHz DMSO): δ=10.10 (s, br, 1H, OH)); 7.28 (d, J=8.2,1H, H3); 7.09 (s, 1H, H4′); 6.96 (m, 2H, H6′ and H7′); 6.91 (s, 1H, H6);6.77 (d, J=8.2, 1H, H4); 6.04 (s, 2H, CH₂O); 3.50 (s, br, 3H, NH₃ ⁺).

[0185] 30. 4-Amino-4′-methoxy-2′-methyl-[1,1′-biphenyl]-2-olhydrochloride

[0186] Bromo derivative used: 1-bromo-4-methoxy-2-methylbenzene

[0187] Yield: 0.016 g (10% of the theoretical)

[0188] ESI-MS: 230 [M+H]⁺ (100)

[0189] 31. 4-Amino-4′-phenoxy-[1,1′-biphenyl]-2-ol hydrochloride

[0190] Bromo derivative used: 1-bromo-4-phenoxybenzene

[0191] Yield: 0.024 g (13% of the theoretical)

[0192] ESI-MS: 276 [M−H]⁺ (100)

[0193] 32. 4-Amino-[1,1′-biphenyl]-2,4′-diol hydrochloride

[0194] Bromo derivative used: 4-bromophenol

[0195] Yield: 0.033 g (23% of the theoretical)

[0196] ESI-MS: 200 [M−H]⁺ (100)

[0197] 33. 4-Amino-2′-methyl-[1,1′-biphenyl]-2,4′-diol hydrochloride

[0198] Bromo derivative used: 4-bromo-3-methylphenol

[0199] Yield: 0.012 g (8% of the theoretical)

[0200] ESI-MS: 216 [M+H]⁺ (100)

[0201] 34. 3′,4-Diamino-[1,1′-biphenyl]-2-ol hydrochloride

[0202] Bromo derivative used: 3-bromoaniline

[0203] Yield: 0.032 g (23% of the theoretical)

[0204] ESI-MS: 199 [M−H]⁺ (100)

[0205] 35. 1-(4′-Amino-2′-hydroxy-1,1′-biphenyl-4-yl)ethanonehydrochloride

[0206] Bromo derivative used: 4-bromoacetophenone

[0207] Yield: 0.016 g (10% of the theoretical)

[0208] ESI-MS: 250 [M+Na]⁺ (100)

[0209] 36. 4-Amino-1,1′:3′,1″-terphenyl-2-ol hydrochloride

[0210] Bromo derivative used: 3-bromo-1,1′-biphenyl

[0211] Yield: 0.050 g (28% of the theoretical)

[0212] ESI-MS: 260 [M−H]⁺ (100)

[0213] 37. 5-Amino-2-(3-pyridinyl)phenol hydrochloride

[0214] Bromo derivative used: 3-bromopyridine

[0215] Yield: 0.067 g (50% of the theoretical)

[0216] ESI-MS: 187 [M+H]⁺ (100)

[0217]¹H-NMR (300 MHz, DMSO): δ=10.88 (s, br, 1H, OH); 9.09 (s, 1H,H2′); 8.81 (d, J=5.5, 1H, H4′); 8.76 (d, J=8.2, 1H, H6′); 8.09 (dd,J=5.5, J=8.2, 1H, H5′); 7.54 (d, J=8.3, 1H, H3); 7.02 (d, J=1.7, 1H,H6); 6.84 (dd, J=1.7, J=8.3, 1H, H4); 4.2 (s, br, 3H, NH₃ ⁺).

[0218] 38. 5-Amino-2-(2-pyridinyl)phenol hydrochloride

[0219] Bromo derivative used: 2-bromopyridine

[0220] Yield: 0.038 g (28% of the theoretical)

[0221] ESI-MS: 187 [M+H]⁺ (100)

[0222] 39. 5-Amino-2-(3-methyl-2-pyridinyl)phenol hydrochloride

[0223] Bromo derivative used: 2-bromo-3-methylpyridine

[0224] Yield: 0.039 g (27% of the theoretical)

[0225] ESI-MS: 201 [M+H]⁺ (100)

[0226] 40. 5-Amino-2-(4-methyl-2-pyridinyl)phenol hydrochloride

[0227] Bromo derivative used: 2-bromo-4-methylpyridine

[0228] Yield: 0.057 g (39% of the theoretical)

[0229] ESI-MS: 201 [M+H]⁺ (100)

[0230] 41. 5-Amino-2-(5-methyl-2-pyridinyl)phenol hydrochloride

[0231] Bromo derivative used: 2-bromo-5-methylpyridine

[0232] Yield: 0.051 g (35% of the theoretical)

[0233] ESI-MS: 201 [M+H]⁺ (100)

[0234] 42. 5-Amino-2-(6-methyl-2-pyridinyl)phenol hydrochloride

[0235] Bromo derivative used: 2-bromo-6-methylpyridine

[0236] Yield: 0.056 g (39% of the theoretical)

[0237] ESI-MS: 201 [M+H]⁺ (100)

[0238] 43. 5-Amino-2-(5-nitro-2-pyridinyl)phenol hydrochloride

[0239] Bromo derivative used: 2-bromo-5-nitropyridine

[0240] Yield: 0.060 g (37% of the theoretical)

[0241] ESI-MS: 230 [M−H]⁺ (100)

[0242] 44. 5-Amino-2-(5-bromo-3-pyridinyl)phenyl hydrochloride

[0243] Bromo derivative used: 3,5-dibromopyridine

[0244] Yield: 0.047 g (26% of the theoretical)

[0245] ESI-MS: 265 [M]⁺ (100)

[0246]¹H-NMR (300 MHz, DMSO): δ=10.54 (s, br, 1H, OH); 8.75 (s, 1H,H2′); 8.67 (s, 1H, H6′); 8.24 (s, 1H, H4′); 7.54 (d, J=8.2, 1H, H3);6.97 (s, 1H, H6); 6.82 (d, J=8.2 1H, H4).

[0247] 45. 5-Amino-2-(5-pyrimidinyl)phenol hydrochloride

[0248] Bromo derivative used: 5-bromopyrimidine

[0249] Yield: 0.067 g (50% of the theoretical)

[0250] ESI-MS: 188 [M+H]⁺ (100)

[0251]¹H-NMR (300 MHz, DMSO): δ=10.74 (s, br, 1H, OH); 9.14 (s, 1H,H2′); 9.00 (s, 2H, H4′ and H6′); 7.52 (d, J=8.1, 1H, H3); 7.10 (d,J=1.6, 1H, H6); 6.93 (dd, J=1.6, J=8.1, 1H, H4);3.76 (s, br, 3H, NH₃ ⁺).

Examples 46 to 90 Hair Colorants

[0252] Hair colorant solutions of the following composition wereprepared: 1.25 mmol of the substance of formula (I) as per Table 1 1.25mmol of the developer as per Table 1 10.0 g of lauryl ether sulfate (28%aqueous solution) 9.0 g of ammonia (22% aqueous solution) 7.8 g ofethanol 0.3 g of ascorbic acid 0.3 g of disodiumethylenediaminetetraacetate hydrate to 100.0 g water, demineralized

[0253] Just before use, 10 g of the above colorant solution was mixedwith 10 g of a 6% hydrogen peroxide solution. The mixture was thenapplied to bleached hair. After an exposure time of 30 minutes at 40°C., the hair was rinsed with water, washed with a commercial shampoo anddried. Table 1 summarizes the resulting colorations. Developer III II4,5-diamino- IV I 2,5-diamino- 1-(2′-hydroxy- 4-amino- Coupler of2,5-diamino- phenylethanol ethyl)pyrazole 3-methyl- Example Formula (I)toluene sulfate sulfate sulfate phenol 90 as per dark dark strawberrylight Example 45 blue blue red pink

Examples 91 to 114 Hair Colorants

[0254] Hair colorant solutions of the following composition wereprepared: X g of 3-aminophenol derivative of formula (I) (coupler K1 toK4 as per Table 4) U g of developer E8 to E15 as per Table 2 Y g ofcoupler K12 to K36 as per Table 4 10.0 g of lauryl ether sulfate (28%aqueous solution) 9.0 g of ammonia (22% aqueous solution) 7.8 g ofethanol 0.3 g of ascorbic acid 0.3 g of disodiumethylenediaminetetraacetate hydrate to 100.0 g water, demineralized

[0255] Just before use, 30 g of the above colorant solution was mixedwith 30 g of a 6% aqueous hydrogen peroxide solution. The mixture wasthen applied to bleached hair. After an exposure time of 30 minutes at40° C., the hair was rinsed with water, washed with a commercial shampooand dried. Table 5 summarizes the resulting colorations. TABLE 2Developers E8 1,4-diaminobenzene E9 2,5-diaminophenylethanol sulfate E103-methyl-4-aminophenol E11 4-amino-2-aminomethylphenol dihydrochlorideE13 N,N-bis-(2′-hydroxyethyl)-p-phenylenediamine sulfate E144,5-diamino-1-(2′-hydroxyethyl)pyrazole sulfate E15 2,5-diaminotoluenesulfate

[0256] TABLE 3 Direct Dyes D2 6-chloro-2-ethylamino-4-nitrophenol D32-amino-6-chloro-4-nitrophenol

[0257] TABLE 4 Couplers K1 4-amino-3′-methyl-[1,1′-biphenyl]-2-ol K24-amino-4′-methyl-3′-nitro-[1,1′-biphenyl]-2-ol K35-amino-2-(3-pyridinyl)phenol K4 5-amino-2-(5-pyrimidinyl)phenol K122-amino-4-(2′-hydroxyethyl)aminoanisole sulfate K131,3-diamino-4-(2′-hydroxyethoxy)benzene sulfate K142,4-diamino-5-fluorotoluene sulfate K18 N-(3-dimethylamino)phenylureaK19 1,3-bis-(2,4-diaminophenoxy)propane tetrahydrochloride K213-aminophenol K22 5-amino-2-methylphenol K233-amino-2-chloro-6-methylphenol K24 5-amino-4-fluoro-2-methylphenolsulfate K25 1-naphthol K31 1,3-dihydroxybenzene K322-methyl-1,3-dihydroxybenzene K33 1-chloro-2,4-dihydroxybenzene K344-(2′-hydroxyethyl)amino-1,2-methylenedioxy- benzene hydrochloride K362-amino-5-methylphenol

[0258] TABLE 5 Hair Colorants Example No. 91 92 93 94 95 96 Dyes (Dyequantity in grams) K1 0.10 0.12 0.05 0.07 0.10 0.12 E8 0.30 E9 0.25 0.20E10 0.10 E15 0.25 0.30 0.25 K12 0.05 K13 0.05 K21 0.05 K22 0.05 K23 0.050.10 0.10 0.10 K25 0.10 K31 0.20 0.15 0.10 0.10 K32 0.20 0.10 K33 0.20K36 0.10 Coloring result blond blond blond blond blond blond Example No.97 98 99 100 101 102 Dyes (Dye quantity in grams) K2 0.10 0.12 0.05 0.070.10 0.12 E8 0.30 E9 0.25 0.20 E10 0.10 E15 0.25 0.30 0.25 K12 0.05 K130.05 K21 0.05 K22 0.05 K23 0.05 0.10 0.10 0.10 K25 0.10 K31 0.20 0.150.10 0.10 K32 0.20 0.10 K33 0.20 K36 0.10 Coloring result blond blondblond blond blond blond Example No. 103 104 105 106 107 108 Dyes (Dyequantity in grams) K3 0.10 0.12 0.05 0.07 0.10 0.12 E8 0.30 E9 0.25 0.20E10 0.10 E15 0.25 0.30 0.25 K12 0.05 K13 0.05 K21 0.05 K22 0.05 K23 0.050.10 0.10 0.10 K25 0.10 K31 0.20 0.15 0.10 0.10 K32 0.20 0.10 K33 0.20K36 0.10 Coloring result blond blond blond blond blond blond Example No.109 110 111 112 113 114 Dyes (Dye quantity in grams) K4 0.10 0.12 0.050.07 0.10 0.12 E8 0.30 E9 0.25 0.20 E10 0.10 E15 0.25 0.30 0.25 K12 0.05K13 0.05 K21 0.05 K22 0.05 K23 0.05 0.10 0.10 0.10 K25 0.10 K31 0.200.15 0.10 0.10 K32 0.20 0.10 K33 0.20 K36 0.10 Coloring result blondblond blond blond blond blond

Examples 115 to 138 Hair Colorants

[0259] Hair colorant solutions of the following composition wereprepared: X g of 3-aminophenol derivative of formula (I) (coupler K1 toK4 as per Table 4) U g of developer E8 to E15 as per Table 2 Y g ofcoupler K11 to K36 as per Table 4 Z g of direct dye D2 and/or D3 as perTable 3 10.0 g of lauryl ether sulfate (28% aqueous solution) 9.0 g ofammonia (22% aqueous solution) 7.8 g of ethanol 0.3 g of ascorbic acid0.3 g of disodium ethylenediaminetetraacetate hydrate to 100.0 g water,demineralized

[0260] Just before use, 30 g of the above colorant cream was mixed with30 g of a 6% aqueous hydrogen peroxide solution. The mixture was thenapplied to hair. After an exposure time of 30 minutes at 40° C., thehair was rinsed with water, washed with a commercial shampoo and dried.Table 6 summarizes the resulting colorations. TABLE 6 Hair ColorantsExample No. 115 116 117 118 119 120 Dyes (Dye quantity in grams) K1 0.601.30 1.15 0.15 0.15 0.15 E8 1.50 E11 0.10 E13 1.60 0.70 E14 0.10 0.10E15 1.80 0.70 0.70 K12 0.50 K14 0.10 K18 0.05 K19 0.10 K23 0.05 0.100.10 0.10 K24 0.15 K31 0.90 1.10 1.10 0.40 0.40 0.40 K34 0.10 D2 0.100.10 0.10 D3 0.05 0.05 0.05 Coloring result black black black brownbrown brown Example No. 121 122 123 124 125 126 Dyes (Dye quantity ingrams) K2 0.60 1.30 1.15 0.15 0.15 0.15 E8 1.50 E11 0.10 E13 1.60 0.70E14 0.10 0.10 E15 1.80 0.70 0.70 K12 0.50 K14 0.10 K18 0.05 K23 0.050.10 0.10 0.10 K24 0.15 K31 0.90 1.10 1.10 0.40 0.40 0.40 K34 0.10 D20.10 0.10 0.10 D3 0.05 0.05 0.05 Coloring result black black black brownbrown brown Example No. 127 128 129 130 131 132 Dyes (Dye quantity ingrams) K3 0.60 1.30 1.15 0.15 0.15 0.15 E8 1.50 E11 0.10 E13 1.60 0.70E14 0.10 0.10 E15 1.80 0.70 0.70 K12 0.50 K14 0.10 K18 0.05 K23 0.050.10 0.10 0.10 K24 0.15 K31 0.90 1.10 1.10 0.40 0.40 0.40 K34 0.10 D20.10 0.10 0.10 D3 0.05 0.05 005 Coloring result black black black brownbrown brown Example No. 133 134 135 136 137 138 Dyes (Dye quantity ingrams) K4 0.60 1.30 1.15 0.15 0.15 0.15 E8 1.50 E11 0.10 E13 1.60 0.70E14 0.10 0.10 E15 1.80 0.70 0.70 K12 0.50 K14 0.10 K18 0.05 K23 0.050.10 0.10 0.10 K24 0.15 K31 0.90 1.10 1.10 0.40 0.40 0.40 K34 0.10 D20.10 0.10 0.10 D3 0.05 0.05 0.05 Coloring result black black black brownbrown brown

[0261] Unless otherwise indicated, the percentages given in the presentpatent application are by weight.

1. Agent for dyeing keratin fibers based on a developer-couplercombination and characterized in that it contains at least one3-aminophenol derivative of formula (I) or a physiologically compatible,water-soluble salt thereof

wherein R1 denotes a group of formula (II) or (III)

wherein R2, R3, R4, R5 and R6 independently of each other denotehydrogen, a halogen atom, a cyano group, hydroxyl group, (C₁-C₄)-alkoxygroup, a phenoxy group, a (C₁-C₄)-hydroxyalkoxy group, a (C₁-C₆)-alkylgroup, a phenyl group, a (C₁-C₄)-alkyl thioether group, a mercaptogroup, a nitro group, an amino group, a (C₁-C₄)-alkylamino group, ahydroxy(C₂-C₄)alkylamino group, a di(C₁-C₄)alkylamino group, adi[hydroxy(C₂-C₄)alkyl]amino group, a [dihydroxy(C₃-C₄)alkyl]-aminogroup, a [hydroxy(C₂-C₄)alkyl]-(C₁-C₄)-alkylamino group, atrifluoromethyl group, a —C(O)H group, a —C(O)CH₃ group, a —C(O)CF₃group, a —Si(CH₃)₃ group, a (C₁-C₄)-hydroxyalkyl group, a(C₂-C₄)-dihydroxyalkyl group, a (C₁-C₄)-aminoalkyl group or a(C₁-C₄)-cyanoalkyl group, or two adjacent R2 to R6 groups form an—O—CH₂—O-bridge; X₁, X₂, X3, X4 and Xs independently of each otherdenote nitrogen or a C—R7 group, C—R8 group, C—R9 group, C—R10 group orC—R11 group, provided that at least one and at the most three of the X₁to X₅ groups denote nitrogen; and R7, R8, R9, R10 and R11 independentlyof each other denote hydrogen, a halogen atom, a cyano group, a(C₁-C₆)-alkyl group, a (C₁-C₄)-alkyl thioether group, a mercapto group,a nitro group, an amino group a (C₁-C₄)-alkylamino group, adi(C₁-C₄)alkylamino group, a trifluoromethyl group, a —C(O)H group, a—C(O)CH₃ group, a —C(O)CF₃ group, a —Si(CH₃)₃ group, a —C(O)—NH₂ group,a (C₁-C₄)-hydroxyalkyl group or a (C₂-C₄)-dihydroxyalkyl group.
 2. Agentaccording to claim 1, characterized in that for the compounds of formula(I) (i) R1 stands for a group of formula (II) with R2 and R6 denotinghydrogen, or (ii) R1 stands for a group of formula (I) with X₁ and X₅denoting C—R7 and C—R11, with R7 and R11 denoting hydrogen.
 3. Agentaccording to claim 1 or 2, characterized in that the compounds offormula (I) are selected from among4-amino-3′-methyl-[1,1′-biphenyl]-2-ol,4-amino-4′-methyl-3′-nitro-[1,1′-biphenyl]-2-ol,4-amino-[1,1′-biphenyl]-2,4′-diol, 5-amino-2-(3-pyridinyl)phenol and5-amino-2-(5-pyrimidinyl)phenol as well as the physiologicallycompatible, water-soluble salts thereof.
 4. Agent according to one ofclaims 1 to 3, characterized in that it contains the 3-aminophenolderivative of formula (1) in an amount from 0.005 to 20 weight percent.5. Agent according to one of claims 1 to 4, characterized in that thedeveloper is selected from the group consisting of 1,4-diaminobenzene,1,4-diamino-2-methylbenzene, 1,4-diamino-2,6-dimethylbenzene,1,4-diamino-3,5-diethylbenzene, 1,4-diamino-2,5-dimethylbenzene,1,4-diamino-2,3-dimethylbenzene, 2-chloro-1,4-diaminobenzene,1,4-diamino-2-(thiophen-2-yl)benzene,1,4-diamino-2-(thiophen-3-yl)benzene,1,4-diamino-2-(pyridin-3-yl)benzene, 2,5-diaminobiphenyl,1,4-diamino-2-methoxymethylbenzene, 1,4-diamino-2-aminomethylbenzene,1,4-diamino-2-hydroxymethylbenzene,1,4-diamino-2-(2-hydroxyethoxy)benzene,2-[2-(acetylamino)ethoxy]-1,4-diaminobenzene, 4-phenylaminoaniline,4-dimethylaminoaniline, 4-diethylaminoaniline, 4-dipropylaminoaniline,4-[ethyl-(2-hydroxyethyl)amino]aniline,4-[di(2-hydroxyethyl)amino]aniline,4-[di(2-hydroxyethyl)amino]-2-methylaniline,4-[(2-methoxy-ethyl)amino]aniline, 4-[(3-hydroxypropyl)amino]aniline,4-[(2,3-dihydroxypropyl)amino]aniline,1,4-diamino-2-(1-hydroxyethyl)benzene,1,4-diamino-2-(2-hydroxyethyl)benzene,1,4-diamino-2-(1-methylethyl)benzene, 1,3-bis-[(4-amin2-hydroxyethyl)amino]-2-propanol, 1,4-bis-[(4-aminophenyl)amino]butane,1,8-bis-(2,5-diaminophenoxy)-3,6-dioxaoctane, 4-aminophenol,4-amino-3-methylphenol, 4-amino-3-(hydroxymethyl)phenol,4-amino-3-fluorophenol, 4-methylaminophenol,4-amino-2-(aminomethyl)phenol, 4-amino-2-(hydroxymethyl)phenol,4-amino-2-fluoro-phenol, 4-amino-2-[(2-hydroxyethyl)amino]-methylphenol,4-amino-2-methylphenol, 4-amino-2-(methoxymethyl)phenol,4-amino-2-(2-hydroxyethyl)phenol, 5-aminosalicylic acid,2,5-diaminopyridine, 2,4,5,6-tetraminopyrimidine,2,5,6-triamino-4-(1H)-pyrimidone,4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole,4,5-diamino-1-(1-methylethyl)-1H-pyrazole,4,5-diamino-1-[(4-methylphenyl)methyl]-1H-pyrazole,1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazole,4,5-diamino-1-methyl-1H-pyrazole, 2-aminophenol, 2-amino-6-methylphenol,2-amino-5-methylphenol and 1,2,4-trihydroxybenzene.
 6. Agent accordingto one of claims 1 to 5, characterized in that besides the compounds offormula (I) it contains at least one additional known coupler selectedfrom the group consisting of N-(3-dimethylaminophenyl)urea,2,6-diaminopyridine, 2-amino-4-[(2-hydroxyethyl)amino]anisole,2,4-diamino-1-fluoro-5-methylbenzene,2,4-diamino-1-methoxy-5-methylbenzene,2,4-diamino-1-ethoxy-5-methylbenzene,2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene,2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxybenzene,2,3-diamino-6-methoxypyridine,3-amino-6-methoxy-2-(methylamino)pyridine,2,6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine,1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)benzene,1,3-diamino-4-(2,3-dihydroxypropoxy)benzene,1,3-diamino-4-(3-hydroxypropoxy)benzene,1,3-diamino-4-(2-methoxyethoxy)benzene,2,4-diamino-1,5-di(2-hydroxyethoxy)benzene,1-(2-aminoethoxy)-2,4-diaminobenzene,2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene,2,4-diaminophenoxyacetic acid, 3-[di(2-hydroxy-2-ethyl)amino]aniline,4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene,5-methyl-2-(1-methylethyl)phenol, 3-[(2-hydroxyethyl)amino]aniline,3-[(2-aminoethyl)amino]aniline, 1,3-di(2,4-diaminophenoxy)propane,di(2,4-diaminophenoxy)methane, 1,3-diamino-2,4-dimethoxybenzene,2,6-bis-(2-hydroxyethyl)aminotoluene, 4-hydroxyindole,3-dimethylaminophenol, 3-diethylaminophenol, 5-amino-2-methylphenol,5-amino-4-fluoro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol,5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichlorophenol,5-amino-2,4-dichlorophenol, 3-amino-2-methylphenol,3-amino-2-chloro-6-methylphenol, 3-aminophenol,2-[(3-hydroxyphenyl)amino]acetamide,5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol,5-[(2-hydroxyethyl)amino]-2-methylphenol,3-[(2-hydroxyethyl)amino]phenol, 3-[(2-methoxyethyl)amino]phenol,5-amino-2-ethylphenol, 5-amino-2-methoxyphenol,2-(4-amino-2-hydroxyphenoxy)ethanol,5-[(3-hydroxypropyl)amino]-2-methylphenol,3-[(2,3-dihydroxypropyl)-amino]-2-methylphenol,3-[(2-hydroxyethyl)amino]-2-methylphenol, 2-amino-3-hydroxypyridine,2,6-dihydroxy-3,4-dimethylpyridine, 5-amino-4-chloro-2-methylphenol,1-naphthol, 2-methyl-1-naphthol, 1,5-dihydroxynaphthalene,1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene,2,7-dihydroxynaphthalene, 2-methyl-1-naphthol acetate,1,3-dihydroxybenzene, 1-chloro-2,4-dihydroxybenzene,2-chloro-1,3-dihydroxybenzene,1,2-dichloro-3,5-dihydroxy-4-methylbenzene,1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline,5-[(2-hydroxyethyl)amino]-1,3-benzodioxole,6-bromo-1-hydroxy-3,4-methylenedioxybenzene, 3,4-diaminobenzoic acid,3,4-dihydro-6-hydroxy-1,4(2H)benzoxazine,6-amino-3,4-dihydro-1,4(2H)benzoxazine, 3-methyl-1-phenyl-5-pyrazolone,5,6-dihydroxyindole, 5,6-dihydroxyindoline, 5-hydroxyindole,6-hydroxyindole, 7-hydroxyindole and 2,3-indolinedione.
 7. Agentaccording to one of claims 1 to 6, characterized in that, based on thetotal amount of colorant, it contains the developers and couplers in atotal amount of 0.005 to 20 weight percent, each.
 8. Agent according toone of claims 1 to 7, characterized in that it contains additionally atleast one direct dye.
 9. Agent according to one of claims 1 to 8,characterized in that it has a pH from 6.5 to 11.5.
 10. Ready-to-useagent for oxidative dyeing of keratin fibers which, in a mediumappropriate for dyeing, contains at least one developer, at least onecoupler and at least one oxidant, characterized in that it contains asthe coupler at least one 3-aminophenol derivative of formula (I)according to one of claims 1 to
 3. 11. Agent according to one of claims1 to 10, characterized in that it is a hair colorant.
 12. 3-Aminophenolderivative of formula (I) or a physiologically compatible, water-solublesalt thereof

wherein R1 denotes a group of formula (II) or (III)

wherein R2, R3, R4, R5 and R6 independently of each other denotehydrogen, a halogen atom, a cyano group, hydroxyl group, (C₁-C₄)-alkoxygroup, a phenoxy group, a (C₁-C₄)-hydroxyalkoxy group, a (C₁-C₆)-alkylgroup, a phenyl group, a (C₁-C₄)-alkyl thioether group, a mercaptogroup, a nitro group, an amino group, a (C₁-C₄)-alkylaMino group, ahydroxy-(C₂-C₄)-alkylamino group, a di(C₁-C₄)-alkylamino group, adi[hydroxy-(C₂-C₄)-alkyl]amino group, a [dihydroxy-(C₃-C₄)alkyl]aminogroup, a [hydroxy-(C₂-C₄)-alkyl]-(C₁-C₄)-alkylamino group, atrifluoromethyl group, a —C(O)H group, a —C(O)CH₃ group, a —C(O)CF₃group, a —Si(CH₃)₃ group, a (C₁-C₄)— hydroxyalkyl group, a(C₂-C₄)-dihydroxyalkyl group, a (C₁-C₄)-aminoalkyl group or a (C₁-C₄)—cyanoalkylgroup, or two adjacent R2 to R6 groups form an —O—CH₂—O—bridge; X₁, X₂, X3, X4 and Xs independently of each other denotenitrogen of a C—R7 group, C—R8 group, C—R9 group, C—R10 group or C—R11group, provided that at least one and at the most three of the X₁ to X₅groups denote nitrogen; and R7, R8, R9, R10 and R11 independently ofeach other denote hydrogen, a halogen atom, a cyano group, a(C₁-C₆)-alkyl group, a (C₁-C₄)-alkyl thioether group, a mercapto group,a nitro group, an amino group, a (C₁-C₄)-alkylamino group, adi(C₁-C₄)-alkylamino group, a trifluoromethyl group, a —C(O)H group, a—C(O)CH₃ group, a —C(O)CF₃ group, a —Si(CH₃)₃ group, a —C(O)—NH₂ group,a (C₁-C₄)-hydroxyalkyl group or a (C₂-C₄)-dihydroxyalkyl group,providing that (i) R1 is not a 2-pyridyl group and (ii) R1 is not a2-hydroxy-4-aminophenyl group.